AU2020253606B2 - Processes for producing Z-1,1,1,4,4,4-Hexafluorobut-2-ene and intermediates for producing same - Google Patents

Description

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PROCESSES FOR PRODUCING Z-1,1,1,4,4,4-HEXAFLUOROBUT-2-ENE AND INTERMEDIATES FOR

PRODUCING SAME TECHNICAL FIELD

The disclosure herein relates to processes for producing Z-1,1,1,4,4,4-

hexafluoro-2-butene, and intermediates useful its production. The disclosure further

provides processes for producing E- and/or Z-1,1,1,4,4,4-hexafluoro-2-chloro-2-butene

BACKGROUND Many industries have been working for the past few decades to find

replacements for the ozone depleting chlorofluorocarbons (CFCs) and

hydrochlorofluorocarbons (HCFCs). The CFCs and HCFCs have been employed in a

wide range of applications, including their use as refrigerants, cleaning agents,

expansion agents for thermoplastic and thermoset foams, heat transfer media, gaseous

dielectrics, aerosol propellants, fire extinguishing and suppression agents, power cycle

working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing

abrasive agents, and displacement drying agents. In the search for replacements for

these versatile compounds, many industries have turned to the use of

hydrofluorocarbons (HFCs). HFCs have zero ozone depletion potential and thus are

not affected by the current regulatory phase-out as a result of the Montreal Protocol.

In addition to ozone depleting concerns, global warming is another environmental

concern in many of these applications. Thus, there is a need for compositions that meet

both low ozone depletion standards as well as having low global warming potentials.

Certain hydrofluoroolefins are believed to meet both goals. Thus there is a need for

manufacturing processes that provide intermediates useful to produce

hydrofluoroolefins and hydrofluoroolefins that contain no chlorine, which

hydrofluoroolefins have low global warming potential.

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INCORPORATION BY REFERENCE All publications, patents, and patent applications mentioned in this specification

are herein incorporated by reference to the same extent as if each individual

publication, patent, or patent application was specifically and individually indicated to be

incorporated by reference. In case of conflict, the present application, including any

definitions herein, will control.

SUMMARY The present disclosure provides processes for the production of hydrofluoroolefin

Z-1,1,1,4,4,4-hexafluorobut-2-ene (Z-HFO-1336mzz, or Z-1336mzz) and intermediates

useful its production.

The present disclosure further provides a process for the production of a product

mixture comprising E- and/or Z-1,1,1,4,4,4-hexafluoro-2-chloro-2-butene, (HCFO-

1326mxz, 1326mxz) comprising contacting 1,1,2,4,4-pentachlorobuta-1,3-dieng (HCC-

2320az) with HF and a fluorination catalyst.

The present disclosure provides a process for the production of Z-1,1,1,4,4,4-

hexafluorobut-2-ene comprising (a) contacting 1,1,2,4,4-pentachlorobuta-1,3-diene with

HF in the vapor phase in the presence of a chlorine source and a fluorination catalyst to

produce a product mixture comprising E- and/or Z-1,1,1,4,4,4-hexafluoro-2-chloro-2-

butene; (b) contacting E- and/or -1,1,1,4,4,4-hexafluoro-2-chloro-2-butene with base

to produce a product mixture comprising 1,1,1,4,4,4-hexafluoro-2-butyne; and (c)

contacting 1,1,1,4,4,4-hexafluoro-2-butyne with hydrogen to produce a product mixture

comprising Z-1,1,1,4,4,4-hexafluoro-2-butene.

In some embodiments, 1,1,2,4,4-pentachlorobuta-1,3-diene (HCC-2320az,

2320az) is produced according to a process comprising dimerization of trichloroethylene

(TCE). A process to produce 2320az comprises contacting TCE in the presence of a

catalyst to produce a product mixture comprising 2320az.

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CI CI CI Cat. H CI CI CI H CI CI

TCE 2320az

In some embodiments, the dimerization of TCE is performed in the presence of

pentachloroethane (CCl3CHCl2, HCC-120), which accelerates the dimerization process.

In certain embodiments, 2320az is produced with a selectivity of at least 80%; in

some embodiments, selectivity is greater than 90% or greater than 95% or greater than

99% or greater than 99.5%. In certain embodiments, 2320az is recovered from the

product mixture. In some embodiments, unreacted TCE is recovered and recycled.

The present disclosure further provides compositions produced according to the

processes disclosed herein.

DETAILED DESCRIPTION As used herein, the terms "comprises," "comprising," "includes," "including,"

"has," "having" or any other variation thereof, are intended to cover a non-exclusive

inclusion. For example, a process, method, article, or apparatus that comprises a list of

elements is not necessarily limited to only those elements but may include other

elements not expressly listed or inherent to such process, method, article, or apparatus.

When an amount, concentration, or other value or parameter is given as either a

range, preferred range or a list of upper preferable values and/or lower preferable

values, this is to be understood as specifically disclosing all ranges formed from any

pair of any upper range limit or preferred value and any lower range limit or preferred

value, regardless of whether ranges are separately disclosed. Where a range of

numerical values is recited herein, unless otherwise stated, the range is intended to

include the endpoints thereof, and all integers and fractions within the range.

By "recovering" it is meant to sufficiently isolate the desired product to make it

available for its intended use, either as a starting material for a subsequent reaction step or, in the case of recovering Z-1,1,1,4,4,4-hexafluoro-2-butene, useful, for example, as a refrigerant or foam expansion agent.

The details of the recovery step will depend on the compatibility of the product

mixture with the reaction conditions of the subsequent reaction step. For example, if the

product is produced in a reaction medium that is different from or incompatible with a

subsequent reaction step, then the recovery step may include separation of the desired

product from the product mixture including the reaction medium. This separation may

occur simultaneously with the contacting step when the desired product is volatile under

the reaction conditions. The volatilization of the desired product can constitute the

isolation and thereby the recovery of the desired product. If the vapors include other

materials intended for separation from the desired product, the desired product may be

separated, by selective distillation, for example.

The steps for recovering the desired product from the product mixture, preferably

comprise separating the desired product from catalyst or other component(s) of the

product mixture used to produce the desired product or produced in the process.

The present disclosure provides, inter alia, processes to produce Z-1336mzz,

and intermediates for producing Z-1336mzz. Such process may use a starting material

comprising 1,1,2,4,4-pentachlorobuta-1,3-diene, which may be produced from

trichloroethylene, one method as set forth herein.

Production of 1,1,2,4,4-pentachlorobuta-1,3-diene (2320az)

1,1,2,4,4-pentachlorobuta-1,3-diene (HCC-2320az, or 2320az) may be produced

in accordance with this disclosure by dimerization of trichloroethylene (TCE). In some

embodiments, there is provided a process to produce a product mixture comprising

2320az, which process comprises contacting TCE with a dimerization catalyst at an

elevated temperature.

In some embodiments, the dimerization catalyst comprises iron. An iron

dimerization catalyst may comprise metallic iron from any source (including a

combination of sources) and may be or comprise iron powder, iron wire, iron screen or

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iron turnings. The iron catalyst may also comprise an iron salt such as ferric chloride or

ferrous chloride (FeCl3 or FeCl2, respectively).

In some embodiments, the dimerization catalyst comprises copper. A copper

dimerization catalyst may comprise metallic copper from any source (including a

combination of sources) and may be or comprise copper powder or copper wire, for

example. The copper catalyst may also comprise a cuprous or a cupric salt such as

cuprous chloride or cupric chloride (CuCI or CuCl2, respectively).

The process is preferably performed in an anhydrous environment. For example,

when ferric chloride is used, the ferric chloride is preferably anhydrous.

In some embodiments, the dimerization catalyst has a particular concentration

with respect to moles of TCE reactant used. As such, in some embodiments wherein

the catalyst comprises a metallic iron catalyst, a ratio of weight of Fe wire (or Fe

powder) catalyst to TCE is from about 0.0001 to about 1. In other embodiments, the

weight ratio of iron catalyst to TCE is from about 0.01 to about 1.

In some embodiments, the dimerization catalyst comprises ferric chloride and the

weight ratio of ferric chloride to TCE is from about 0.00001 to about 1. For example, the

weight ratio of ferric chloride to TCE is from about 0.00001 to about 0.002, while in

another example, the weight ratio is from about 0.00005 to about 0.001. In yet another

example, a weight ratio of ferric chloride to TCE is from about 0.0001 to about 1, while

in a further example, the ratio of ferric chloride to TCE is from about 0.00015 to about 1.

In some embodiments, trichloroethylene is contacted with a dimerization catalyst

and pentachloroethane. Pentachloroethane (HCC-120) accelerates the reaction to

produce the product mixture comprising 2320az. In certain embodiments, a weight ratio

of HCC-120 to TCE is from about 0.001 to about 1. In other embodiments, the weight

ratio of HCC-120 to TCE is from about 0.005 to about 1.

The dimerization of TCE is performed in at an elevated temperature, for example

at a temperature in the range of about 210 to about 235°C. The temperature may be

greater than 200°C. The temperature may be less than 245°C.

Pressure is typically autogenous.

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Contact (residence) time is typically about 0.5 to 10 hours.

In some embodiments, conversion of TCE is at least 15% or at least 30%, or at

least 50%. In some embodiments, selectivity to 2320az is at least 80%, or at least 85%,

or at least 90%.

Byproducts in the dimerization reaction may include tetrachloroethane isomers,

tetrachlorobutadiene isomers, hexachlorobutene isomers, trichloroethylene oligomers.

The product mixture comprising 2320az may further comprise E-1,1,2,3,4-pentachloro-

1,3-butadiene or Z-1,1,2,3,4-pentachloro-1,3-butadiene. Thus, in one embodiment

there is a composition comprising 1,1,2,4,4-pentachlorobuta-1,3-diene, E-1,1,2,3,4-

pentachlorobuta-1,3-diene, and Z-1,1,2,3,4-pentachlorobuta-1,3-diene.

The process may further comprise recovering 2320az from the product mixture

prior to use of the recovered 2320az as a starting material in a process to produce E-

and Z-1326mxz, 1,1,1,4,4,4-hexafluoro-2-butyne and HFO-Z-1336mzz, for example, as

set forth herein.

Processes for recovering 2320az from the product mixture may include one or

any combination of purification techniques, such as distillation, that are known in the art.

By "recovering" 2320az from the product mixture, a product comprising at least 95% or

at least 97% or at least 99% 2320az is produced.

In certain embodiments, the process to produce 2320az may further comprise

recovering trichloroethylene from the product mixture and recycling the recovered

trichloroethylene to the dimerization process as set forth herein.

In certain embodiments, the process to produce 2320az may further comprise

recovering hexachlorobutene isomers from the product mixture and recycling the

recovered hexachlorobutene isomers to the dimerization process as set forth herein.

In certain embodiments, the process to produce 2320az may further comprise

recovering pentachloroethane from the product mixture and recycling the recovered

pentachloroethane to the dimerization process as set forth herein.

Other products, if present, such as E-1,1,2,3,4-pentachloro-1,3-butadiene and Z-

1,1,2,3,4-pentachloro-1,3-butadiene may also be recovered.

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Production of E- and Z-1,1.1.4.4,4-hexafluoro-2-chloro-2-butene (EIZ-1326mxz)

There is provided herein a fluorination process comprising contacting 1,1,2,4,4-

pentachlorobuta-1,3-diene (2320az) with HF, in the presence of a fluorination catalyst

comprising a metal halide and a chlorine source, to provide a product mixture

comprising E- and Z-1,1,1,4,4,4-hexafluoro-2-chloro-2-butene,

Fluorination catalyst comprises at least one metal halide, metal oxide or metal

oxyhalide. This reaction is performed in the vapor phase. The process produces a

product mixture comprising E- and Z-1,1,1,4,4,4-hexafluoro-2-chloro-2-butene.

As used herein, the term "halide" refers to fluorides, chlorides, and bromides.

Examples of suitable metals include nickel, chromium, iron, scandium, yttrium,

lanthanum, titanium, zirconium, hafnium, vanadium, molybdenum, tungsten,

manganese, rhenium, ruthenium, osmium, cobalt, palladium, copper, zinc, tantalum,

antimony, aluminum, tin, and lead. It is noted, as defined herein, antimony is a metal.

Examples of metal halides include nickel halides, chromium halides, iron halides,

scandium halides, yttrium halides, lanthanum halides, titanium halides, zirconium

halides, hafnium halides, vanadium halides, molybdenum halides, tungsten halides,

manganese halides, rhenium halides, ruthenium halides, osmium halides, cobalt

halides, palladium halides, copper halides, zinc halides, antimony halides, tantalum

halides, aluminum halides, tin halides, and lead halides. In an embodiment, the metal

halide is nickel halide, iron halide, or chromium halide or combination thereof is used as

a catalyst with or without support on activated carbon. In another embodiment, the

metal halide is a bromide or chloride. In still another embodiment, the halide is a

chloride. In another embodiment, the metal halide is nickel chloride, iron chloride, or

chromium chloride or combination thereof.

Examples of metal oxides include chromium oxide, aluminum oxide. Metal

oxyhalides may also be used as fluorination catalysts.

The fluorination catalysts may be unsupported or supported on activated carbon.

The activated carbon may be unwashed or be acid washed or base washed.

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The term "activated carbon" includes any carbon with a relatively high surface

area such as from about 50 to about 3000 m² or from about 100 to about 2000 m² (e.g.

from about 200 to about 1500 m² or about 300 to about 1000 m². The activated carbon

may be derived from any carbonaceous material, such as coal (e.g. charcoal), nutshells

(e.g. coconut) and wood. Any form of activated carbon may be used, such as

powdered, granulated and pelleted activated carbon.

In some embodiments, the activated carbon has been washed with at least one

basic solution to remove silicates. For example, the activated carbon is washed with

alkali hydroxide or alkaline earth hydroxide or ammonium hydroxide. Examples of basic

solutions which have been used to wash the activated carbon include sodium

hydroxide, ammonium hydroxide, potassium hydroxide, and the like.

The fluorination process is performed in the presence of a chlorine source. The

chlorine source may be chosen from (i) a catalyst comprising a metal chloride or a metal

oxychloride, such as a catalyst comprising chromium chloride (CrCl3) either as the metal

chloride or as chromium chloride supported on carbon, or (ii) chlorine (Cl2), which is

added to the process when the fluorination catalyst comprises a metal halide or metal

oxyhalide wherein the halide is fluoride or bromide or when the catalyst is a metal oxide.

Optionally chlorine (Cl2) is added when the catalyst is a metal chloride or metal

oxychloride.

In one embodiment, the fluorination catalyst comprises a metal chloride or metal

oxychloride. In another embodiment the fluorination catalyst does not comprise a metal

chloride or metal oxychloride and the process is performed in the presence of chlorine

(Cl2). When chlorine (Cl2) is present, the molar ratio of chlorine (as Cl2) to 2320az is

typically from about 0.5:1 to about 2:1. A preferred molar ratio of chlorine to 2320az is

from about 1.1:1 to about 1:1.

The molar ratio of HF to 2320az, HF:2320az, in some embodiments is from about

1:1 to about 35:1. In other embodiments, the molar ratio of HF to 2320az is from about

1:1 to about 25:1. HF may be added in an amount of 10 to 30 moles per mole of

2320az. In some embodiments, the ratio of HF:2320az:Cl2 is 10-30:1:1.

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The process is performed at effective temperatures and pressures. In an

embodiment, the process is performed in the vapor phase at a temperature ranging

from about 250 to about 425°C. In another embodiment, the process is performed at a

temperature ranging from 275 to about 400°C. In still another embodiment, the process

is performed at a temperature ranging from about 300 to about 375°C, and in another

embodiment from about 325 to about 350°C.

In an embodiment, the process is performed in the vapor phase at a pressure

ranging from about 0 psig to about 200 psig. In another embodiment, the pressure

ranges from about 30 psig to about 150 psig, and in another embodiment, the pressure

ranges from about 40 psig to about 80 psig.

In an embodiment the process is performed at a temperature ranging from about

275 to about 375°C and at a pressure ranging from about 0 psig to about 160 psig, and

in another embodiment temperature ranging from about 300 to about 350°C and at a

pressure ranging from about 0 psig to about 80 psig.

In a preferred embodiment, 2320az is vaporized, optionally in the presence of

HF, and fed to a vapor phase reactor along with HF and Cl2.

The process may further comprise recovering EIZ-1326mxz from the product

mixture prior to use of the recovered EIZ-1326mxz as a starting material in a process to

produce 1,1,1,4,4,4-hexafluoro-2-butyne. Processes for recovering EIZ-1326mxz from

the product mixture may include one or any combination of purification techniques, such

as distillation, that are known in the art. By "recovering" EIZ-1326mxz from the product

mixture, a product comprising at least 95% or at least 97% or at least 99% EIZ-

1326mxz is produced. There is no need to separate the E- and Z-1326mxz isomers.

The product mixture comprising E- and Z-1,1,1,4,4,4-hexafluoro-2-chloro-2-

butene may also comprise E- and/or Z-1,1,1,4,4,4-hexafluoro-2-butene. In the event

either E- or Z-1,1,1,4,4,4-hexafluoro-2-butene is present in the product mixture, each

may be recovered for use as a product or reactant in another process.

Production of 1,1,1,4,4,4-hexafluoro-2-butyne

The present disclosure provides processes for dehydrochlorination of E- and Z-

1326mxz at temperatures well below 100°C using a basic aqueous solution in

combination with quaternary alkylammonium salts as a phase transfer catalyst.

The present disclosure further provides a process comprising contacting E-

and/or Z-1326mxz with base to produce a product mixture comprising 1,1,1,4,4,4-

hexafluoro-2-butyne (CF3C=CCF3) in a dehydrochlorination reaction. The base is

preferably a basic aqueous medium. This reaction step is preferably performed in the

presence of a catalyst. Preferably the basic aqueous medium comprises a solution of

an alkali metal hydroxide or alkali metal halide salt or other base in water. Preferably

the catalyst is a phase transfer catalyst.

As used herein, phase transfer catalyst is intended to mean a substance that

facilitates the transfer of ionic compounds between an organic phase and an aqueous

phase. In this step, the organic phase comprises the E- and/or Z-1326mxz reactant,

and the aqueous phase comprises the basic aqueous medium. The phase transfer

catalyst facilitates the reaction of these dissimilar and incompatible components.

While various phase transfer catalysts may function in different ways, their

mechanism of action is not determinative of their utility in the present invention provided

that the phase transfer catalyst facilitates the dehydrochlorination reaction.

A phase transfer catalyst as used herein is a quaternary alkylammonium salt

wherein the alkyl groups are alkyl chains having from four to twelve carbon atoms. In

one embodiment, the quaternary alkyl ammonium salt is a tetrabutylammonium salt.

The anions of the salt can be halides such as chloride or bromide, hydrogen sulfate, or

any other commonly used anion.

In some embodiments, at least one alkyl group of the quaternary alkylammonium

salt contains at least 8 carbons. An example of quaternary alkylammonium salt wherein

three alkyl groups contain at least 8 carbon atoms includes trioctylmethylammonium

chloride. Aliquat 336 is a commercially available phase transfer catalyst which

contains trioctylmethylammonium chloride. An example of quaternary alkylammonium

salt wherein four alkyl groups contain at least 8 carbon atoms includes

tetraoctylammonium salt. The anions of such salts may be halides such as chloride or

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bromide, hydrogen sulfate, or any other commonly used anion. Specific quaternary

alkylammonium salts include tetraoctylammonium chloride, tetraoctylammonium

hydrogen sulfate, tetraoctylammonium bromide, methytrioctylammonium chloride,

methyltrioctylammonium bromide, tetradecylammonium chloride, tetradecylammonium

bromide, and tetradodecylammonium chloride.

Other compounds commonly thought of as phase transfer catalysts in other

applications, including crown ethers, cryptands or non-ionic surfactants alone, do not

have a significant effect on conversion or the rate of the dehydrochlorination reaction in

the same fashion.

The Z- and E- isomers of 1,1,1,4,4,4-hexafluoro-2-chloro-2-butene exhibit

significantly different reactivities with respect to dehydrochlorination, and have different

requirements for what functions as an effective phase transfer catalyst in this reaction.

Dehydrochlorination of the Z- isomer of 1,1,1,4,4,4-hexafluoro-2-chloro-2-butene

Z-1326mxz, can be effected with quaternary alkylammonium salts wherein the alkyl

groups are alkyl chains having from four to twelve carbon atoms. The anions of the salt

can be halides such as chloride or bromide, hydrogen sulfate, or any other commonly

used anion. In one embodiment, the quaternary alkyl ammonium salt is a

tetrabutylammonium salt. In another embodiment, the quaternary alkylammonium salt

is a tetrahexylammonium salt. In another embodiment, the quaternary alkylammonium

salt is a tetraoctylammonumium salt. In yet another embodiment, the quaternary

alkylammonium salt is a trioctylmethylammonumium salt.

Dehydrochlorination of the E-isomer of 1,1,1,4,4,4-hexafluoro-2-chloro-2-butene

E-1326mxz, can be effected with quaternary alkylammonium salts, wherein the alkyl

groups are alkyl chains having at least one alkyl chain of 8 carbons or more. In another

embodiment, the quaternary alkylammonium salt has three alkyl chains of 8 carbons or

more, such as trioctylmethylammonium salt. In yet another embodiment, the quaternary

alkylammonium salt is a tetraoctylammonumium salt. In yet another embodiment, the

quaternary ammonium salt is a tetradecylammonium salt. In yet another embodiment,

the quaternary alkylammonium salt is a tetradodecylammonium salt. The anions of the

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salt can be halides such as chloride or bromide, hydrogen sulfate, or any other

commonly used anion.

In yet another embodiment, dehydrochlorination of E-1326mxz can be effected

with quaternary alkylammonium salts, wherein the alkyl groups are alkyl chains having

from four to twelve carbon atoms, and in the presence of a non-ionic surfactant. The

non-ionic surfactants can be ethoxylated nonylphenols, and ethoxylated C12 to C15

linear aliphatic alcohols. Suitable non-ionic surfactants include Bio-soft® N25-9 and

Makon® 10 are from Stepan Company.

In one embodiment, the quaternary alkylammonium salts is added in an amount

of from 0.5 mole percent to 2 mole percent of 1326mxz. In another embodiment, the

quaternary alkylammonium salts is added in an amount of from 1 mole percent to 2

mole percent of 1326mxz. In yet another embodiment, the quaternary alkylammonium

salts is added in an amount of from 1 mole percent to 1.5 mole percent of 1326mxz.

In one embodiment, the dehydrochlorination of Z- or E-1326mxz is conducted in

the presence of an alkali metal halide salt. In one embodiment, the alkali metal is

sodium or potassium. In one embodiment, the halide is chloride or bromide. In one

embodiment, the alkali metal halide salt is sodium chloride. Without wishing to be

bound by any particular theory, it is believed that the alkali metal halide salt stabilizes

the phase transfer catalyst. Although the dehydrochlorination reaction itself produces

alkali metal chloride, and in particular sodium chloride if sodium hydroxide is used as

the base, addition of extra sodium chloride provides a further effect of increasing the

yield of hexafluoro-2-butyne.

Addition of alkali metal halide salt also reduces the amount of fluoride ion

measured in the water effluent from the reaction. Without wishing to be bound by any

particular theory, the presence of fluoride is believed to result from decomposition of

either 1326mxz starting material, or 1,1,1,4,4,4-hexafluoro-2-butyne product.

In several samples, the amount of fluoride ion found in the water effluent from the

dehydrochlorination is about 6000 ppm. In several examples, using from 30 to 60

equivalents of sodium chloride per mole of phase transfer catalyst, the amount of

fluoride ion in the water effluent is reduced to 2000 ppm. In one embodiment, the alkali

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metal halide is added at from 25 to 100 equivalents per mole of phase transfer catalyst.

In another embodiment, the alkali metal halide is added at from 30 to 75 equivalents per

mole of phase transfer catalyst. In yet another embodiment, the alkali metal halide is

added at from 40 to 60 equivalents per mole of phase transfer catalyst.

In one embodiment, the reaction is conducted at a temperature of from about 60

to 90°C. In another embodiment, the reaction is conducted at 70°C.

As used herein, the basic aqueous solution is a liquid (whether a solution,

dispersion, emulsion, or suspension and the like) that is primarily an aqueous liquid

having a pH of over 7. In some embodiments the basic aqueous solution has a pH of

over 8. In some embodiments, the basic aqueous solution has a pH of over 10. In

some embodiments, the basic aqueous solution has a pH of 10-13. In some

embodiments, the basic aqueous solution contains small amounts of organic liquids

which may be miscible or immiscible with water. In some embodiments, the liquid

medium in the basic aqueous solution is at least 90% water. In one embodiment the

water is tap water; in other embodiments the water is deionized or distilled.

The base in the aqueous basic solution is selected from the group consisting of

hydroxide, oxide, carbonate, or phosphate salts of alkali, alkaline earth metals and

mixtures thereof. In one embodiment, bases which may be used lithium hydroxide,

sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, calcium

oxide, sodium carbonate, potassium carbonate, trisodium phosphate, disodium

hydrogenphosphate, sodium dihydrogen phosphate, tripotassium phosphate,

dipotassium hydrogenphosphate, potassium dihydrogen phosphate, and mixtures

thereof.

The product 1,1,1,4,4,4-hexafluoro-2-butyne (boiling point -25°) may be

recovered from the product mixture by distillation, wherein the butyne vaporizes from

the aqueous medium and can then be condensed. Any unconverted E- and/or Z-

1326mxz can be recovered from the organic phase of the product mixture and recycled

for the dehydrochlorination process.

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Production of Z-1,1.1.4.4,4-hexafluoro-2-butene

The present disclosure further provides a hydrogenation process comprising

contacting 1,1,1,4,4,4-hexafluoro-2-butyne with hydrogen to produce a product mixture

comprising Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-1336mzz). This process is preferably

performed in the presence of an alkyne-to-alkene catalyst.

In some embodiments the hydrogenation of 1,1,1,4,4,4-hexafluoro-2-butyne is

performed as a batch process in the liquid phase.

In some embodiments the hydrogenation of 1,1,1,4,4,4-hexafluoro-2-butyne is

performed as a continuous process in the vapor phase.

In some embodiments, an alkyne-to-alkene catalyst is a palladium catalyst, such

as palladium dispersed on aluminum oxide or titanium silicate, doped with silver and/or

a lanthanide. The loading of palladium dispersed on the aluminum oxide or titanium

silicate is relatively low. In some embodiments, the palladium loading is from about 100

ppm to about 5000 ppm. In other embodiments, the palladium loading is from about

200 ppm to about 5000 ppm. In some embodiments, the palladium catalyst is doped

with at least one of silver, cerium or lanthanum. In some embodiments, the mole ratio

of cerium or lanthanum to palladium is from about 2:1 to about 3:1. In some

embodiments the mole ratio of silver to palladium is about 0.5:1.0.

Other embodiments of alkyne-to-alkene catalyst is Lindlar catalyst, which is a

heterogeneous palladium catalyst on a calcium carbonate support, which has been

deactivated or conditioned with a lead compound. The lead compound may be lead

acetate, lead oxide, or any other suitable lead compound. In some embodiments, the

catalyst is produced by reduction of a palladium salt in the presence of a slurry of

calcium carbonate, followed by the addition of the lead compound. In some

embodiments, the palladium salt in palladium chloride.

In other embodiments, the Lindlar catalyst is further deactivated or conditioned

with quinoline. The amount of palladium on the support is typically about 5% by weight

but may be any catalytically effective amount. In other embodiments, the amount of

palladium on the support in the Lindlar catalyst is greater than 5% by weight. In yet

WO wo 2020/206279 PCT/US2020/026612

other embodiments, the amount of palladium on the support may be from about 5% by

weight to about 1% by weight.

In some embodiments, the amount of the catalyst used is from about 0.5% by

weight to about 4% by weight of the amount of the 1,1,1,4,4,4-hexafluoro-2-butyne In

other embodiments, the amount of the catalyst used is from about 1% by weight to

about 3% by weight of the amount of the butyne. In yet other embodiments, the amount

of the catalyst used is from about 1% to about 2% by weight of the amount of the

butyne.

In some embodiments, this reaction step is a batch reaction and is performed in

the presence of a solvent. In one such embodiment, the solvent is an alcohol. Typical

alcohol solvents include ethanol, i-propanol and n-propanol. In other embodiments, the

solvent is a fluorocarbon or hydrofluorocarbon. Typical fluorocarbons or

hydrofluorocarbons include (1,1,2,2,3,4,5,5,5-decafluoropentane and 1,1,2,2,3,3,4-

heptafluorocyclopentane.

In some embodiments, reaction of the 1,1,1,4,4,4-hexafluoro-2-butyne with

hydrogen is preferably performed with addition of hydrogen in portions, with increases in

the pressure of the vessel of no more than about 100 psi (0.69 MPa) with each addition.

In other embodiments, the addition of hydrogen is controlled so that the pressure in the

vessel increases no more than about 50 psi (0.35 MPa) with each addition. In some

embodiments, after enough hydrogen has been consumed in the hydrogenation

reaction to convert at least 50% of the butyne to Z-1336mzz, hydrogen may be added in

larger increments for the remainder of the reaction. In other embodiments, after enough

hydrogen has been consumed in the hydrogenation reaction to convert at least 60% of

the butyne to the desired butene, hydrogen may be added in larger increments for the

remainder of the reaction. In yet other embodiments, after enough hydrogen has been

consumed in the hydrogenation reaction to convert at least 70% of the butyne to desired

butene, hydrogen may be added in larger increments for the remainder of the reaction.

In some embodiments, the larger increments of hydrogen addition may be 300 psi (2.07

MPa). In other embodiments, the larger increments of hydrogen addition may be 400

psi i 2.76 MPa).

PCT/US2020/026612

In some embodiments, the molar ratio is about 1 mole of hydrogen to about 1

mole of 1,1,1,4,4,4-hexafluoro-2-butyne. In other embodiments, the molar ratio is from

about 0.9 mole to about 1.3 mole, hydrogen to butyne. In yet other embodiments, the

amount of hydrogen added is from about 0.95 mole of hydrogen to about 1.1 moles of

butyne. In yet other embodiments, the amount of hydrogen added is from about 0.95

moles of hydrogen to about 1.03 moles of butyne.

In some embodiments, the hydrogenation is performed at ambient temperature

(15°C to 25°C). In other embodiments, the hydrogenation is performed at above

ambient temperature. In yet other embodiments, the hydrogenation is performed at

below ambient temperature. In yet other embodiments, the hydrogenation is performed

at a temperature of below about 0°C.

In an embodiment of a continuous process, a mixture of 1,1,1,4,4,4-hexafluoro-2-

butyne and hydrogen is passed through a reaction zone containing the catalyst. A

reaction vessel, e.g., a metal tube, may be used, packed with the catalyst to form the

reaction zone. In some embodiments, the molar ratio of hydrogen to the butyne is about

1:1. In other embodiments of a continuous process, the molar ratio of hydrogen to the

butyne is less than 1:1. In yet other embodiments, the molar ratio of hydrogen to the

butyne is about 0.67:1.0.

In some embodiments of a continuous process, the reaction zone is maintained

at ambient temperature. In other embodiments of a continuous process, the reaction

zone is maintained at a temperature of 30°C. In yet other embodiments of a continuous

process, the reaction zone is maintained at a temperature of about 40°C.

In some embodiments of a continuous process, the flow rate of 1,1,1,4,4,4-

hexafluoro-2-butyne and hydrogen is maintained so as to provide a residence time in

the reaction zone of about 30 seconds. In other embodiments of a continuous process,

the flow rate of the butyne and hydrogen is maintained so as to provide a residence

time in the reaction zone of about 15 seconds. In yet other embodiments of a

continuous process, the flow rate of butyne and hydrogen is maintained SO as to provide

a residence time in the reaction zone of about 7 seconds.

PCT/US2020/026612

It will be understood, that residence time in the reaction zone is reduced by

increasing the flow rate of 1,1,1,4,4,4-hexafluoro-2-butyne and hydrogen into the

reaction zone. As the flow rate is increased this will increase the amount of butyne

being hydrogenated per unit time. Since the hydrogenation is exothermic, depending

on the length and diameter of the reaction zone, and its ability to dissipate heat, at

higher flow rates it may be desirable to provide a source of external cooling to the

reaction zone to maintain a desired temperature.

The conditions of the contacting step, including the choice of catalyst, are

preferably selected to produce Z-1336mzz at a selectivity of at least 85%, more

preferably at least 90%, and most preferably at least 95%.

In some embodiments, upon completion of a batch-wise or continuous

hydrogenation process, the Z-1336mzz may be recovered through any conventional

process, including for example, fractional distillation. Unconverted hexafluoro-2-butyne

may be recovered and recycled to the hydrogenation process. In other embodiments,

upon completion of a batch-wise or continuous hydrogenation process, the Z-1336mzz

is of sufficient purity to not require further purification steps.

EXAMPLES Materials

Trichloroethylene, ferric chloride, chromium chloride, alumina chloride, cupric

chloride, chlorine, pentachloroethane (HCC-120), trioctylmethylammonium chloride

(Aliquat 336), NaOH, K2HPO4 and KH2PO4, and Lindlar catalyst are available from

Sigma Aldrich, St. Louis, MO. Hydrogen fluoride and E-1,1,1,4,4,4-hexafluoro-2-butene

are available from Synquest Labs, Inc., Alachua, FL. 10% chrome chloride on carbon

catalyst is available from BASF, Iselin, NJ.

GC analysis for Examples 1-4 was performed using Agilent 5975GC, RESTEK

Rtx-1 column.

PCT/US2020/026612

Example 1: Preparation of 1,1,2,4,4-pentachlorobuta-1,3-diene (HCC-2320az)

Trichloroethylene (100 g, 0.76 mol) was added to a shaker tube containing 30 mg

anhydrous FeCl3. The reaction mixture was heated at 230°C for 2 hrs. The reactor

content was cooled to room temperature and analyzed by GC to determine the conversion

and selectivity. Results are provided in Table 1.

Example 2: Preparation of 1,1,2,4,4-pentachlorobuta-1,3-diene (HCC-2320az)

Trichloroethylene (100g g, 0.76 mol) was added to a shaker tube containing 1 g iron

wire. The reaction mixture was heated at 230°C for 2 hrs. The reactor content was cooled

to room temperature and analyzed by GC to determine the conversion and selectivity.

Results are provided in Table 1.

Example 3: Preparation of 1,1,2,4,4-pentachlorobuta-1,3-diene (HCC-2320az)

Trichloroethylene (100 g, 0.76 mol) was added to a shaker tube containing 20 mg

anhydrous FeCl3 and 1 g HCC-120. The reaction mixture was heated at 230°C for 2 hrs.

The reactor content was cooled to room temperature and analyzed by GC to determine

the conversion and selectivity. Results are provided in Table 1.

Example 4: Preparation of 1,1,2,4,4-pentachlorobuta-1,3-diene (HCC-2320az)

Trichloroethylene (100g, 0.76 mol) was added to a shaker tube containing 1 g iron

wire and 1 g HCC-120. The reaction mixture was heated at 230°C for 2 hrs. The reactor

content was cooled to room temperature and analyzed by GC to determine the conversion

and selectivity. Results are provided in Table 1.

Table 1. Trichloroethylene Dimerization to 2320az

Time Conversion Example Catalyst (hours) /Selectivity (%)

1 FeCl3 (30 mg) 16 26.9 / 81.6

2 Fe wire (1 g) 8 28.0 / 86.7

3 FeCl3 (20 mg) / HCC-120 (1g) 2 35.4 / 84.3

4 Fe wire (1g) / HCC-120 (1 g) 2 32.3 / 87.4

WO wo 2020/206279 PCT/US2020/026612

As can be seen from Table 1, the presence of HCC-120 increases conversion rate

of trichloroethylene to 2320az when using FeCl3 or Fe wire catalyst.

Example 5: Preparation of E- and Z-1,1,1,4,4,4-hexafluoro-2-chloro-2-butene

An Inconel tube® (0.5 inch OD, 15 inch length, 0.34 in wall thickness) was filled

with 12 CC (6.45 g g) of 10% chrome chloride on carbon catalyst. The reactor was heated

in a Lindberg furnace to 250°C and 2320az was fed at 0.09 ml/hour and HF gas at 5.4

sccm (standard cubic centimeters per minute) through a vaporizer controlled at 200°C.

Over the course of the run, the temperature was raised to 325°C. All of the experiments

were carried out at 1-2 psig. The effluent of the reactor is analyzed online using an

Agilent® 6890 GC/5973 MS and a Restek® PC2618 5% Krytox CBK-D/60/80 6 meter X

2mm ID 1/8" OD packed column purged with helium at 30 sccm. Run conditions are provided in Table 2. Data is shown in Table 3, and samples are taken in hourly intervals.

Table 2: Run Conditions for Vapor Phase Fluorination of 2320az

Furnace Pressure, Liquid, N2, sccm HF, sccm Contact Time, Sample No. Temp., °C psi ml//hr sec

1 1.4 0.09 3.13 5.40 51.2 249

2 250 1.4 0.09 3.10 5.40 51.3

3 250 1.3 0.09 3.13 5.40 50.8

4 250 1.3 0.09 3.13 5.40 50.8

5 250 1.0 0.09 3.09 5.40 50.1

6 275 0.9 0.09 0.09 3.10 5.40 47.4

7 275 0.9 0.09 3.05 5.40 47.7

8 275 0.9 0.09 0.09 3.10 5.40 47.4

9 300 1.0 0.09 3.10 5.40 45.7

10 300 1.0 0.09 3.10 5.40 45.6

11 300 1.0 0.09 3.14 5.40 45.4

12 325 0.9 0.09 3.09 5.40 43.5 43.5

13 325 325 1.0 0.09 0.09 3.09 5.40 43.8

14 325 1.0 0.09 0.09 3.07 5.40 43.9

Unknowns

1.20 1.20 4.45 3.88 6.56 3.65 2.77 2.88 3.77 4.58 4.49 4.94 3.47 3.64

356mff

0.00 0.00 0.00 0.88 0.89 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 mole%) as (expressed 2320az of Fluorination Phase Vapor from Products 3: Table mole%) as (expressed 2320az of Fluorination Phase Vapor from Products 3: Table 346mdf

0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

338mff

7.56 6.83 1.17 0.48 0.56 0.16 0.28 0.53 0.92 2.30 2.71 3.80 3.80 4.49

1327 0.00 0.00 0.00 0.00 6.86 3.99 3.30 3.37 2.65 0.00 3.72 0.00 3.84 0.00

1325 0.00 0.00 0.00 0.00 0.00 3.55 3.47 1.89 1.77 0.25 0.00 0.00 1.51 5.51

1316mxx

0.00 0.00 0.00 0.00 0.00 0.15 0.23 0.48 0.61 0.97 1.12 1.27 0.94 0.96

E-1336mzz E-1336mzz

24.90 13.58 31.68 13.93 12.59 19.45 17.85 24.12 7.86 0.00 3.88 4.68 5.53 7.42

Z-1336mzz Z-1336mzz

0.00 0.00 0.00 0.41 0.46 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

E-1326mxz E-1326mxz

2.12 2.41 1.69 2.24 4.09 3.32 3.23 3.05 3.40 3.26 3.02 3.39 3.10 2.97

Z-1326mxz Z-1326mxz

64.23 75.98 84.26 80.58 83.34 81.96 78.64 77.76 73.08 70.58 66.90 67.00 63.82 61.01

SampleNo. Sample No.

10 11 12 13 14 1 2 3 4 5 6 7 8 9 wo 2020/206279 WO PCT/US2020/026612 PCT/US2020/026612

Example 6: Preparation of 1,1,1,4,4,4-Hexafluoro-2-butyne

NaOH aqueous solution (12 mL, 0.12 mol) was added to the mixture of Z-1326

(20 g, 0.1 mol) and water (18 mL) in the presence of tetra-n-butylammonium bromide

(0.45 g, 0.001325 mol) at 35°C. The reaction temperature was raised to 70°C after

the addition, and gas chromatography was used to monitor the reaction. The reaction

was completed after 1 hour and 15.4 g product (conversion: 100%; yield: 95%) was

collected in a dry ice trap. Results are provided in Table 4.

Example 7: Preparation of 1,1,1,4,4,4-Hexafluoro-2-butyne

NaOH aqueous solution (12 mL, 0.12 mol) was added to the mixture of Z-

1326mxz (20 g, 0.1 mol) and water (18 mL) in the presence of tetra-n-butylammonium

hydrogensulfate (0.43 g, 0.001325 mol) at 35°C. The reaction temperature was raised

to 70°C after the addition, and gas chromatography was used to monitor the reaction.

The reaction was completed after 1 hour and 11 product (conversion: 100%; yield:

71%) was collected in a dry ice trap. Results are provided in Table 4.

Example 8: Preparation of 1,1,1,4,4,4-Hexafluoro-2-butyne

NaOH aqueous solution (12 mL, 0.12 mol) was added to the mixture of Z-

1326mxz (20 g, 0.1 mol) and water (18 mL) in the presence of Aliquat 336 (0.53 g,

0.001325 mol) at 35°C. The reaction temperature was raised to 70°C after the

addition, and gas chromatography was used to monitor the reaction. The reaction was

completed after 1 hour and 15.6 product (conversion: 100%; yield: 96%) was collected

in a dry ice trap. Results are provided in Table 4.

Example 9: Preparation of 1,1,1,4,4,4-Hexafluoro-2-butyne

NaOH aqueous solution (12 mL, 0.12 mol) was added to the mixture of E-

1326mxz (20 g, 0.1 mol) and water (18 mL) in the presence of Aliquat® 336 (0.53 g,

0.001325 mol) at 42°C. The reaction temperature was raised to 70°C after the

addition, and gas chromatography was used to monitor the reaction. The reaction was

completed after 1 hours and 15.8 g product (conversion: 100%; yield: 98%) was

collected in a dry ice trap. Results are provided in Table 4.

wo 2020/206279 WO PCT/US2020/026612 PCT/US2020/026612

Example 10: Preparation of1,1,1,4,4,4-Hexafluoro-2-butyne

NaOH aqueous solution (12 mL, 0.12 mol) was added to the mixture of E-

1326mxz (20 g, 0.1 mol) and water (18 mL) in the presence of tetra-n-butylammonium

bromide (0.45 g, 0.001325 mol) at 42°C. The reaction temperature was raised to 70°C

after the addition, and gas chromatography was used to monitor the reaction. The

reaction was not completed after seven hours. 12.6 g product (conversion: 78%; yield:

78%) was collected in a dry ice trap. Results are provided in Table 4.

Example 11: Preparation of 1,1,1,4,4,4-Hexafluoro-2-butyne

NaOH aqueous solution (12 mL, 0.12 mol) was added to the mixture of E-

1326mxz (20 g, 0.1 mol) and water (18 mL) in the presence of tetra-n-butylammonium

hydrogen sulfate (0.43 g, 0.001325 mol) at 42°C. The reaction temperature was raised

to 70°C after the addition, and gas chromatography was used to monitor the reaction.

The reaction was not completed after seven hours. 12.6 g product (conversion: 77%;

yield: 77%) was collected in a dry ice trap. Results are provided in Table 4.

Example 12: Preparation of 1,1,1,4,4,4-Hexafluoro-2-butyne

NaOH aqueous solution (12 mL, 0.12 mol) was added to the mixture of E-

1326mxz (20 g, 0.1 mol) and water (18 mL) in the presence of tetraoctylammonium

bromide (0.72 g, 0.001325 mol) at 42°C. The reaction temperature was raised to 70°C

after the addition, and gas chromatography was used to monitor the reaction. The

reaction was completed after six and half hours. 15.6 g product (conversion: 100%;

yield: 95%) was collected in a dry ice trap. Results are provided in Table 4.

Example 13: Preparation of 1,1,1,4,4,4-Hexafluoro-2-butyne

NaOH aqueous solution (12 mL, 0.12 mol) was added to the mixture of E-

1326mxz (20 g, 0.1 mol) and water (18 mL) in the presence of tetraoctylammonium

chloride (0.43 g, 0.001325 mol) at 42°C. The reaction temperature was raised to 70°C

after the addition, and gas chromatography was used to monitor the reaction. After

five and half hours, 15.2 g product (conversion: 95%; yield: 93%) was collected in a

dry ice trap. Results are provided in Table 4.

wo 2020/206279 WO PCT/US2020/026612 PCT/US2020/026612

Example 14: Preparation of f1,1,1,4,4,4-Hexafluoro-2-butyne

NaOH aqueous solution (12 mL, 0.12 mol) was added to the mixture of E-

1326mxz (20 g, 0.1 mol) and water (18 mL) in the presence of tetra-n-butylammonium

chloride (0.37 g, 0.001325 mol) at 42°C. The reaction temperature was raised to 70°C

after the addition, and gas chromatography was used to monitor the reaction. After

twenty-three hours, 14.8 g product (conversion: 90%; yield: 87%) was collected in a

dry ice trap. Results are provided in Table 4.

Example 15: Preparation of 1,1,1,4,4,4-Hexafluoro-2-butyne

NaOH aqueous solution (12 mL, 0.12 mol) was added to the mixture of E-

1326mxz (20 g, 0.1 mol) and water (18 mL) in the presence of tributylmethylammonium chloride (0.31 g, 0.001325 mol) at 42°C. The reaction

temperature was raised to 70°C after the addition, and gas chromatography was used

to monitor the reaction. After twenty-three hours, 8 g product (conversion: 59%; yield:

49%) was collected in a dry ice trap. Results are provided in Table 4.

Example 16: Preparation of 1,1,1,4,4,4-Hexafluoro-2-butyne

NaOH aqueous solution (12 mL, 0.12 mol) was added to the mixture of ZE-

1326mxz (a mixture of 50% Z-1326mxz and 50% E-1326mxz) (20 g, 0.1 mol) and water (18 mL) in the presence of tetrabutylammonium bromide (0.45 g, 0.001325 mol)

and Bio-soft® N25-9 (0.7 g) at 38°C. The reaction temperature was raised to 70°C

after the addition, and gas chromatography was used to monitor the reaction. The

reaction was completed after 5 hours. 13 g product (conversion:100% yield: 80%)

was collected in a dry ice trap. Results are provided in Table 4.

Example 17: Preparation of 1,1,1,4,4,4-Hexafluoro-2-butyne

NaOH aqueous solution (12 mL, 0.12 mol) was added to the mixture of ZE-

1326mxz (a mixture of 50% Z-1326mxz and 50% E-1326mxz) (20 g, 0.1 mol) and water (18 mL) in the presence of tetrabutylammonium bromide (0.45 g, 0.001325 mol)

and Makon® 10 (0.7 g) at 38°C. The reaction temperature was raised to 70°C after the

addition, and gas chromatography was used to monitor the reaction. The reaction was

PCT/US2020/026612

completed after 5 hours. 11.2 g product (conversion: 100%; yield: 69%) was collected

in a dry ice trap. Results are provided in Table 4.

Example 18: Preparation of 1,1,1,4,4,4-Hexafluoro-2-butyne

10 M NaOH aqueous solution (12 mL, 0.12 mol) was added over 30 min to a

ZE-1326mxz (a mixture of 50% Z-1326mxz and 50% E-1326mxz) (20 g, 0.1 mol)

and water (18 mL) in the presence of NaCI (2.3 g, 0.0393 mol) and Aliquat 336

(0.53 g, 0.001325 mol) at 37°C. When the addition was complete, the reaction

temperature was raised to 70°C after the addition, and gas chromatography was

used to monitor the reaction. The reaction was completed after 1 hour and 20

minutes and the water layer was submitted for wt% fluoride analysis. Results are

provided in Table 4.

Example 19: Preparation of 1,1,1,4,4,4-Hexafluoro-2-butyne

NaOH aqueous solution (12 mL, 0.12 mol) was added over 30 min to a ZE-

1326mxz (a mixture of 50% Z-1326mxz and 50% E-1326mxz) (20 g, 0.1 mol) and

water (18 mL) in the presence of NaCI (4.6 g, 0.0786 mol) and Aliquat® 336 (0.53 g,

0.001325 mol) at 37°C. When the addition was complete, the reaction temperature

was raised to 70°C after the addition, and gas chromatography was used to monitor

the reaction. The reaction was completed after 1 hour and 20 minutes and the water

layer was submitted for wt% fluoride analysis. Results are provided in Table 4.

Example 20: Preparation of 1,1,1,4,4,4-Hexafluoro-2-butyne

NaOH aqueous solution (12 mL, 0.12 mol) was added over 30 min to a

mixture of ZE-1326mxz (a mixture of 50% Z-1326mxz and 50% E-1326mxz) (20 g,

0.1 mol) and water (18 mL) in the presence of NaCI (3.45 g, 0.0590 mol) and

Aliquat 336 (0.53 g, 0.001325 mol) at 37°C. When the addition was complete, the

reaction temperature was raised to 70°C after the addition, and gas chromatography

was used to monitor the reaction. The reaction was completed after 2 hours and the

water layer was submitted for wt% fluoride analysis. Results are provided in Table

4.

PCT/US2020/026612

Comparative Example A

NaOH aqueous solution (12 mL, 0.12 mol) was added to the mixture of ZE-

1326mxz (a mixture of 50% Z-1326mxz and 50% E-1326mxz) (20 g, 0.1 mol) and water (18 mL) at 37°C. The reaction temperature was raised to 70°C after the addition,

and gas chromatography was used to monitor the reaction. After thirty-one hours. 0.36

g product (conversion: 2.2%; yield: 2.2%) was collected in a dry ice trap. Results are

provided in Table 4.

Comparative Example B

NaOH aqueous solution (6 mL, 0.06 mol) was added to the mixture of ZE-

1326mxz (a mixture of 50% Z-1326mxz and 50% E-1326mxz) (10 g, 0.05 mol) and

water (18 mL) at 37°C in the presence of 15-Crown-5 (0.65 g, 0.003 mol). The reaction

temperature was raised to 70°C after the addition, and gas chromatography was used

to monitor the reaction. The reaction was not completed after thirty hours. 1.16 g

product (conversion: 14%; yield: 14%) was collected in a dry ice trap. Results are

provided in Table 4.

Comparative Example C

NaOH aqueous solution (12 mL, 0.12 mol) was added to the mixture of ZE-

1326mxz (a mixture of 50% Z-1326mxz and 50% E-1326mxz) (20 g, 0.1 mol) and water (18 mL) at 37°C in the presence of Makon® 10 (0.7g). The reaction temperature

was raised to 70°C after the addition, and gas chromatography was used to monitor

the reaction. The reaction was not completed after twenty-two hours. 1.09 g product

(conversion: 17%; yield: 6.8%) was collected in a dry ice trap. Results are provided

in Table 4.

PCT/US2020/026612

Table 4. Results of Examples 6-20, Comparative Examples A-C

Example 1326 Time (hr) Conv. (%) Yield (%)

1 100 100 6 Z 7 1 100 100 Z 8 1 100 100 Z 9 1 100 100 E 10 E 7 78 11.1

11 E 6.5 77 11

12 E 6.5 100 15.4

13 E 5.5 95 17.3

14 E 23 90 3.9

15 E 23 59 2.6

16 ZE 5 100 20

17 ZE 4 100 25

18 ZE 1.3 100 75 75

19 ZE 1.3 100 75

20 ZE 2 100 50

Comp. A ZE 21 2.2 0.07 0.07

Comp. B ZE 30 14 0.47 0.47

Comp. C ZE 22 17 0.77

Notes: Time is in hours; Conv. refers to weight% conversion of 1326; Yield is

weight% yield of 1,1,1,4,4,4-hexafluoro-2-butyne produced.

Example 21: Preparation of Z-1,1,1,4,4,4-hexafluoro-2-butene

1,1,1,4,4,4-Hexafluoro-2-butyne produced according to Example 9 was

reacted with hydrogen to produce the desired Z-isomer of 1,1,1,4,4,4-hexafluoro-2-

butene by the following procedure: 5g of Lindlar (5% Pd on CaCO3 poisoned with

lead) catalyst was charged in 1.3 L rocker bomb. 480g (2.96 mole) of hexafluoro-2-

butyne was charged in the rocker. The reactor was cooled (-78°C) and evacuated.

After the bomb was warmed to room temperature, H2 was added slowly, by

increments which did not exceed Ap= 50 psi (0.35 MPa). A total of 3 moles H2 were added to the reactor. A gas chromatographic analysis of the crude product indicated the mixture consisted of CF3C=CCF3 (0.236%), trans-isomer E-CF3CH=CHCF3

(0.444%), saturated CF3CH2CH2CF3 (1.9%) CF2=CHCI, impurity from starting

butyne, (0.628%), cis-isomer Z-CF3CH=CHCF3 (96.748%).

Distillation of the crude product afforded 287g (59%yield) of 100% pure cis-

CF3CH=CHCF3 (boiling point 33.3°C). MS: 164 [MI], 145 [M-19], 95 [CF3CH=CH], 69

[CF3]. NMR 1H: 6.12 ppm (multiplet), 19F: -60.9 ppm (triplet J=0.86Hz). The

selectivity of this reaction to the formation of the Z-isomer was 96.98%. The Z-

isomer was recovered by distillation.

Other Embodiments 1. In some embodiments, the present disclosure provides a fluorination

process for producing a product mixture comprising E- and Z-1,1,1,4,4,4-hexafluoro-

2-chloro-2-butene comprising contacting 1,1,2,4,4-pentachlorobuta-1,3-diene with

HF in the vapor phase in the presence of a chlorine source and a fluorination

catalyst and comprising a metal halide to produce a product mixture comprising E-

and Z-1,1,1,4,4,4-hexafluoro-2-chloro-2-butene.

2. In some embodiments, the fluorination catalyst comprises a metal

chloride.

3. In some embodiments, the fluorination catalyst does not comprise a

metal chloride and the process is performed in the presence of chlorine(Cl2).

4. In some embodiments, the fluorination catalyst comprises a metal

chloride chosen from nickel chloride, iron chloride, or chromium chloride or

combination thereof.

5. In some embodiments, the fluorination catalyst is unsupported.

6. In some embodiments, the fluorination catalyst is supported on

activated carbon.

7. In some embodiments, the ratio of chlorine (as Cl2) to 1,1,2,4,4-

pentachlorobuta-1,3-diene is 0.5:1 to 2:1.

28 wo 2020/206279 WO PCT/US2020/026612 PCT/US2020/026612

8. In some embodiments, the molar ratio of HF to 1,1,2,4,4-

pentachlorobuta-1,3-diene, HF:2320az, is from about 1:1 to about 35:1.

9. In some embodiments, the fluorination process is performed at a

temperature in the range of 250 to 425°C.

10. In some embodiments, the fluorination process is performed at a

pressure in the range of 0 to 200 psi (0 to 1.4 MPa).

11. In some embodiments, the process of any embodiment 1-10 further

comprises producing 1,1,2,4,4-pentachlorobuta-1,3-diene by contacting

trichloroethylene with a dimerization catalyst comprising iron to produce a product

mixture comprising 1,1,2,4,4-pentachlorobuta-1,3-diene.

12. In some embodiments, in the process of any embodiment 11,

trichloroethylene is contacted with a dimerization catalyst comprising iron and

pentachloroethane.

13. In some embodiments, the present disclosure provides a process for

producing a product mixture comprising E- and dZ-1,1,1,4,4,4-hexafluoro-2-chloro-2-

butene comprising:

(a) producing 1,1,2,4,4-pentachlorobuta-1,3-diene by contacting

trichloroethylene with a dimerization catalyst to produce a product mixture

comprising 1,1,2,4,4-pentachlorobuta-1,3-diene; and

(b) contacting 1,1,2,4,4-pentachlorobuta-1,3-diene with HF in the

vapor phase in the presence of a chlorine source and a fluorination catalyst

comprising a metal halide to produce a product mixture comprising E- and Z-

1,1,1,4,4,4-hexafluoro-2-chloro-2-butene

14. In some embodiments, the present disclosure provides a process for

producing a product mixture comprising E- and Z-1,1,1,4,4,4-hexafluoro-2-chloro-2-

butene comprising:

(a) producing 1,1,2,4,4-pentachlorobuta-1,3-diene by contacting

trichloroethylene with a dimerization catalyst and pentachloroethane to wo 2020/206279 WO PCT/US2020/026612 produce a product mixture comprising 1,1,2,4,4-pentachlorobuta-1,3-diene; and and

(b) contacting 1,1,2,4,4-pentachlorobuta-1,3-diene with HF in the

vapor phase in the presence of a chlorine source and a fluorination catalyst

comprising a metal halide to produce a product mixture comprising E- and Z-

11,1,4,4,4-hexafluoro-2-chloro-2-butene.

15. In some embodiments, the process of embodiment 13 or 14 further

comprises recovering 1,1,2,4,4-pentachlorobuta-1,3-diene from the product mixture

of step (a).

16. In some embodiments, the process of embodiment 13 or 14 or 15

further comprises recovering trichloroethylene from the product mixture of step (a).

17. In some embodiments, the present disclosure provides a process to

produce Z-1,1,1,4,4,4-hexafluorobut-2-ene, comprising:

(a) contacting trichloroethylene with a dimerization catalyst to

produce a product mixture comprising 1,1,2,4,4-pentachlorobuta-1,3-diene;

(b) contacting 1,1,2,4,4-pentachlorobuta-1,3-diene with HF in the

vapor phase in the presence of a chlorine source and a fluorination catalyst

comprising a metal halide to produce a product mixture comprising E- and Z-

1,1,1,4,4,4-hexafluoro-2-chloro-2-butene;

(c) contacting E- and/or Z-1,1,1,4,4,4- hexafluoro-2-chloro-2-butene

with base to produce a product mixture comprising 1,1,1,4,4,4-hexafluoro-2-

butyne; and

(d) contacting 1,1,1,4,4,4-hexafluoro-2-butyne with H2 to produce a

product mixture comprising Z-1,1,1,4,4,4-hexafluorobut-2-ene.

18. In some embodiments, the process of embodiment 17 further

comprises recovering 1,1,2,4,4-pentachlorobuta-1,3-diene from the product mixture

of step (a).

PCT/US2020/026612

19. In some embodiments, the process of embodiment 17 or 19 further

comprises recovering trichloroethylene from the product mixture of step (a).

20. In some embodiments, embodiments 17, 18 and 19 further comprise

recovering E- and Z-1,1,1,4,4,4-hexafluoro-2-chloro-2-butene from the product

mixture of step (b).

21. In some embodiments, embodiments 17, 18, 19 and 20 further

comprise recovering 1,1,1,4,4,4-hexafluoro-2-butyne from the product mixture of

step (c).

22. In some embodiments, embodiments 17, 18, 19, 20 and 21 further

comprise recovering Z-1,1,1,4,4,4-hexafluoro-2-butene from the product mixture of

step (d).

It is to be understood that while the invention has been described in

conjunction with the detailed description thereof, the foregoing description is

intended to illustrate and not limit the scope of the invention, which is defined by the

scope of the appended claims. Other aspects, advantages, and modifications are

within the scope of the following claims. It should be appreciated by those persons

having ordinary skill in the art(s) to which the present invention relates that any of

the features described herein in respect of any particular aspect and/or embodiment

of the present invention can be combined with one or more of any of the other

features of any other aspects and/or embodiments of the present invention

described herein, with modifications as appropriate to ensure compatibility of the

combinations. Such combinations are considered to be part of the present invention

contemplated by this disclosure.

Claims (13)

Claims 04 Mar 2024 2020253606 04 Mar 2024 Claims What is claimed is:

1. 1. A process for producing a product mixture comprising E- and Z- 1,1,1,4,4,4-hexafluoro-2-chloro-2-butene comprising contacting 1,1,2,4,4- pentachlorobuta-1,3-diene with HF in the vapor phase in the presence of a chlorine source and a fluorination catalyst and to produce a product mixture comprising E- and 2020253606

Z-1,1,1,4,4,4-hexafluoro-2-chloro-2-butene.

2. 2. The process of claim 1, wherein the fluorination catalyst comprises a metal chloride or metal oxychloride wherein the catalyst is the chlorine source.

3. 3. The process of claim 1, wherein the fluorination catalyst comprises a metal halide or metal oxyhalide wherein the halide is not chloride, or the catalyst is a metal oxide and the chlorine source is chlorine (Cl2).

4. 4. The process of claim 3, wherein the molar ratio of chlorine to 1,1,2,4,4- pentachlorobuta-1,3-diene is 1 to 10.

5. The process of any one of claims 1, 3 or 4, wherein the process is performed in the presence of chlorine (Cl2).

6. 6. The process of any one of claims 1-5, wherein the molar ratio of HF to 1,1,2,4,4-pentachlorobuta-1,3-diene is from about 1 to about 35.

7. 7. The process of any one of claims 1-6, further comprising producing 1,1,2,4,4-pentachlorobuta-1,3-diene by contacting trichloroethylene with a dimerization catalyst comprising iron to produce a product mixture comprising 1,1,2,4,4- pentachlorobuta-1,3-diene.

8. 8. The process of claim 7, wherein trichloroethylene is contacted with a dimerization catalyst comprising iron and pentachloroethane.

9. 9. A process for producing a product mixture comprising E- and Z- 1,1,1,4,4,4-hexafluoro-2-chloro-2-butene comprising:

32

(a) producing 1,1,2,4,4-pentachlorobuta-1,3-diene by contacting 04 Mar 2024 2020253606 04 Mar 2024

trichloroethylene with a dimerization catalyst to produce a product mixture comprising 1,1,2,4,4-pentachlorobuta-1,3-diene; and

(b) contacting 1,1,2,4,4-pentachlorobuta-1,3-diene with HF in the vapor phase in the presence of a fluorination catalyst comprising a metal halide to produce a product mixture comprising E- and Z-1,1,1,4,4,4-hexafluoro-2-chloro- 2020253606

2-butene. 2-butene.

10. A process for producing a product mixture comprising E- and Z- 1,1,1,4,4,4-hexafluoro-2-chloro-2-butene comprising:

(a) producing 1,1,2,4,4-pentachlorobuta-1,3-diene by contacting trichloroethylene with a dimerization catalyst and pentachloroethane to produce a product mixture comprising 1,1,2,4,4-pentachlorobuta-1,3-diene; and

(b) contacting 1,1,2,4,4-pentachlorobuta-1,3-diene with HF in the vapor phase in the presence of a fluorination catalyst comprising a metal halide to produce a product mixture comprising E- and Z-1,1,1,4,4,4-hexafluoro-2-chloro- 2-butene.

11. The process of claim 9 or 10, further comprising recovering 1,1,2,4,4- pentachlorobuta-1,3-diene from the product mixture of step (a); or recovering trichloroethylene from the product mixture of step (a).

12. A process to produce Z-1,1,1,4,4,4-hexafluorobut-2-ene, comprising:

(a) contacting trichloroethylene with a dimerization catalyst to produce a product mixture comprising 1,1,2,4,4-pentachlorobuta-1,3-diene;

(b) contacting 1,1,2,4,4-pentachlorobuta-1,3-diene with HF in the vapor phase in the presence of a fluorination catalyst comprising a metal halide to produce a product mixture comprising E- and Z-1,1,1,4,4,4-hexafluoro-2-chloro- 2-butene;

(c) contacting E- and/or Z-1,1,1,4,4,4- hexafluoro-2-chloro-2-butene with base to produce a product mixture comprising 1,1,1,4,4,4-hexafluoro-2- butyne; and

33

(d) contacting 1,1,1,4,4,4-hexafluoro-2-butyne with H2 to produce a 04 Mar 2024 2020253606 04 Mar 2024

product mixture comprising Z-1,1,1,4,4,4-hexafluorobut-2-ene.

13. The process of claim 12, further comprising recovering 1,1,2,4,4- pentachlorobuta-1,3-diene from the product mixture of step (a); or recovering trichloroethylene from the product mixture of step (a); or recovering E- and Z- 1,1,1,4,4,4-hexafluoro-2-chloro-2-butene from the product mixture of step (b); or 2020253606

recovering 1,1,1,4,4,4-hexafluoro-2-butyne from the product mixture of step (c) or recovering Z-1,1,1,4,4,4-hexafluoro-2-butene from the product mixture of step (d).